4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)

Detalhes bibliográficos
Autor(a) principal: Rocha, Zênis Novais da
Data de Publicação: 2001
Outros Autores: Ferreira, Kleber Queiroz, Silva, Maristela, Oliveira, Érica Cristina de, Chiericato, Glaico, Tfouni, Elia
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UFBA
Texto Completo: http://www.repositorio.ufba.br/ri/handle/ri/7627
Resumo: p. 5385-5392
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spelling Rocha, Zênis Novais daFerreira, Kleber QueirozSilva, MaristelaOliveira, Érica Cristina deChiericato, GlaicoTfouni, EliaRocha, Zênis Novais daFerreira, Kleber QueirozSilva, MaristelaOliveira, Érica Cristina deChiericato, GlaicoTfouni, Elia2012-12-17T18:53:32Z2012-12-17T18:53:32Z20010020-1669http://www.repositorio.ufba.br/ri/handle/ri/7627v. 40, n. 21p. 5385-5392The synthesis, UV−vis spectra, and electrochemical behavior of the nitrile-bonded trans-[RuIICl(cyclam)(4-NCpyH+)](BF4)2 (4-Ncpy = 4-cyanopyridine; cyclam = 1,4,8,11-tetraazacyclotetradecane) and of trans-[RuIIICl(cyclam)(NHC(O)-4-pyH+)]2+ are described. The UV−vis spectrum of the Ru(II) nitrile complex shows a MLCT band at 548 nm at pH 1, which is shifted to 440 nm at pH 6, for the unprotonated species. trans-[RuIICl(cyclam)(4-NCpyH+)]2+ was electrolytically oxidized (+600 mV vs Ag/AgCl) at pH 1 to Ru(III), followed by hydrolysis (k = 0.25 s-1) of the coordinated nitrile to give trans-[RuIIICl(cyclam)(NHC(O)-4-pyH+)]2+, in which the amide is deprotonated and coordinated through nitrogen. The identity of the species is pH dependent, the nitrogen-bonded amide prevailing at low pH (<7), but the oxygen-bonded amide is formed through linkage isomerization at higher pH (>8). Reduction of trans-[RuIIICl(cyclam)(NHC(O)-4-pyH)]2+ in acidic media does not result in fast aquation (k = 2.4 × 10-5 s-1) as for other amides on ruthenium(II) pentaammine, but instead linkage isomerization occurs, resulting in the oxygen-bonded species, with an estimated rate constant of 2 × 10-2 s-1, smaller than in the pentaammine analogues.Submitted by Suelen Reis (suelen_suzane@hotmail.com) on 2012-12-17T18:53:32Z No. of bitstreams: 1 ic0011563.pdf: 174002 bytes, checksum: e85d7e3802d62304864907ec17f47125 (MD5)Made available in DSpace on 2012-12-17T18:53:32Z (GMT). No. of bitstreams: 1 ic0011563.pdf: 174002 bytes, checksum: e85d7e3802d62304864907ec17f47125 (MD5) Previous issue date: 2001http://dx.doi.org/10.1021/ic0011563reponame:Repositório Institucional da UFBAinstname:Universidade Federal da Bahia (UFBA)instacron:UFBA4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)Inorganic Chemistryinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleenginfo:eu-repo/semantics/openAccessORIGINALic0011563.pdfic0011563.pdfapplication/pdf174002https://repositorio.ufba.br/bitstream/ri/7627/1/ic0011563.pdfe85d7e3802d62304864907ec17f47125MD51LICENSElicense.txtlicense.txttext/plain1762https://repositorio.ufba.br/bitstream/ri/7627/2/license.txt1b89a9a0548218172d7c829f87a0eab9MD52TEXTic0011563.pdf.txtic0011563.pdf.txtExtracted texttext/plain47201https://repositorio.ufba.br/bitstream/ri/7627/3/ic0011563.pdf.txt3961c59d816ef0c7ead4d527d9c6de5fMD53ri/76272022-07-05 14:03:03.939oai:repositorio.ufba.br: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Repositório InstitucionalPUBhttp://192.188.11.11:8080/oai/requestopendoar:19322022-07-05T17:03:03Repositório Institucional da UFBA - Universidade Federal da Bahia (UFBA)false
dc.title.pt_BR.fl_str_mv 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
dc.title.alternative.pt_BR.fl_str_mv Inorganic Chemistry
title 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
spellingShingle 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
Rocha, Zênis Novais da
title_short 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
title_full 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
title_fullStr 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
title_full_unstemmed 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
title_sort 4-Cyanopyridine and amide-N and amide-o linkage isomers of 4-pyridinecarboxamide on Trans-Chloro(1,4,8,11 tetraazacyclotetradecane)ruthenium(II/III)
author Rocha, Zênis Novais da
author_facet Rocha, Zênis Novais da
Ferreira, Kleber Queiroz
Silva, Maristela
Oliveira, Érica Cristina de
Chiericato, Glaico
Tfouni, Elia
author_role author
author2 Ferreira, Kleber Queiroz
Silva, Maristela
Oliveira, Érica Cristina de
Chiericato, Glaico
Tfouni, Elia
author2_role author
author
author
author
author
dc.contributor.author.fl_str_mv Rocha, Zênis Novais da
Ferreira, Kleber Queiroz
Silva, Maristela
Oliveira, Érica Cristina de
Chiericato, Glaico
Tfouni, Elia
Rocha, Zênis Novais da
Ferreira, Kleber Queiroz
Silva, Maristela
Oliveira, Érica Cristina de
Chiericato, Glaico
Tfouni, Elia
description p. 5385-5392
publishDate 2001
dc.date.issued.fl_str_mv 2001
dc.date.accessioned.fl_str_mv 2012-12-17T18:53:32Z
dc.date.available.fl_str_mv 2012-12-17T18:53:32Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://www.repositorio.ufba.br/ri/handle/ri/7627
dc.identifier.issn.none.fl_str_mv 0020-1669
dc.identifier.number.pt_BR.fl_str_mv v. 40, n. 21
identifier_str_mv 0020-1669
v. 40, n. 21
url http://www.repositorio.ufba.br/ri/handle/ri/7627
dc.language.iso.fl_str_mv eng
language eng
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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dc.source.none.fl_str_mv reponame:Repositório Institucional da UFBA
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